Sulfonic acid functionalized metal-organic framework (S-IRMOF-3): a novel catalyst for sustainable approach towards the synthesis of acrylonitriles.

ABSTRACT: A sulfonic acid functionalized metal-organic framework (S-IRMOF-3) has been synthesized by dropwise addition of chlorosulfonic acid (0.5 mL) in IRMOF-3 (1 g) containing 20 mL of CHCl₃ at 0 °C under simple stirring. The catalyst was applied in Knoevenagel condensation of various aromatic and hetero-aromatic aldehydes forming acrylonitrile derivatives. The catalyst was characterized thoroughly by using FT-IR, XRD, ¹³C MAS NMR, SEM, EDX, elemental mapping, TEM, BET, NH₃-TPD and TGA/DTA techniques. The presence of characteristic bands at 1694 cm^-1, 1254-769 cm^-1 and 1033 cm^-1 in the FT-IR spectrum, 2θ ≃ 6.7° and 9.8° in the XRD pattern and δ = 31.79, 39.55, 129.61, 131.46 (4C, CH), 133.54, 140.07 (2C), 167.71, 171.47 ppm (2C, 2C[double bond, length as m-dash]O) in the solid state ¹³C MAS NMR spectrum confirmed the successful formation of catalyst. This new eco-friendly approach resulted in a significant improvement in the synthetic efficiency (90-96% yield), high product purity, and minimizing the production of chemical wastes without using highly toxic reagents for the synthesis of acrylonitriles with selectivity for (Z)-isomer. Steric interactions seem to have an influence on the control of the Z-configurational isomers. By performing DFT calculations, it was found that the (Z)-isomer 3a is stabilized by 1.64 kcal mol^-1 more than the (E)-isomer. The catalyst could be reused for five consecutive cycles without substantial loss in catalytic activity.

SUBMITTER: Rather RA 

PROVIDER: S-EPMC9064389 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature